[0001] The present invention relates to a new process for extracting apolar compounds, in
particular n-paraffins, from mixtures which contain them, which process uses a gas
under supercritic conditions, which acts in countercurrent in a tower of novel conception
and containing a series of perforated trays, particularly suitable for such types
of extractions.
[0002] The present invention relates also to the tower used in the above said process.
[0003] The process disclosed in the present invention is particularly suitable for separating
unreacted n-paraffins from the remainder of the reaction mixture in the processes
of sulfonation of said n-paraffins.
[0004] The fractionation of complex mixtures into their individual components has always
been one of the most serious problems from an industrial view point, in that the modern
industrial processes have got more and more refined in the preparation of products
as free as possible from byproducts and unreacted substances.
[0005] Such a demand is particularly felt in the processes of sulfonation of n-paraffins,
in which said n-paraffins should be separated as extensively as possible from the
reacted products not only owing to self-explanatory economic reasons, but also because
their presence is undesired for the uses the paraffinsulfonic acids are destined to.
[0006] The solutions generally proposed for separations of byproducts of the above described
type are still now the operations of liquid/liquid extraction, which are carried out
by using equipment with the most different characteristics.
[0007] Such is, e.g., the case disclosed in European patent N. 131,913, according to which
the reaction products coming from the reactor of sulfonation of n-paraffins are separated
by means of a double treatment of extraction with isopropanol and methylene chloride
followed by the end distillation of the phase rich of n-paraffins.
[0008] Considerably cheaper and more selective processes than the liquid/liquid process
have been proposed recently for extracting various components from reaction mixtures
which contain them; such systems have recourse to fluids kept under supercritic conditions,
i.e., under pressure and temperature conditions which are above the critic conditions
of said fluids.
[0009] The fluids which operate under such conditions are extremely sensitive to the changes
in the pressure of the system in which they operate. In fact, small differences in
the pressure or in the temperature of a supercritic fluid cause considerable changes
to take place in its density.
[0010] If, besides the above, one considers the fact that the supercritic fluids have a
viscosity similar to those of the gases, one will understand why such supercritic
fluids are being used more and more extensively in the extraction operations. As the
solvent power of a fluid is strongly depending on the density of the same fluid, small
differences in pressure in the region of supercritic temperature and pressure values
cause, owing to the above outlined reasons, changes in the solubility and selectivity
of the same fluid, thus considerably increasing the speed of extraction and release
of the solute in the extraction processes.
[0011] A process of extraction of n-paraffins from their mixtures with sulfonated paraffins
based on the use of supercritic CO₂ is disclosed in European Patent No. 0261700.
In order to carry out such a process, the use is provided of an extraction apparatus
which is essentially constituted by an extractor to which the mixture is charged,
which contains the product which has to be extracted with supercritic CO₂, and a separator
in which CO₂, separated from the extracted substance, is recycled to the extractor
by means of metering pumps, after being previously condensed.
[0012] This process, advantageous owing to the use of a supercritic gas as compared to the
well-known liquid/liquid systems, is however carried out batchwise, which not always
results in immediate operating advantages.
[0013] Such advantages could evidently be achieved if the benefits deriving from the use
of a supercritic gas were combined with an extraction methodology performed in counter-current
mode, using from time to time apparatuses endowed with the characteristics suitable
for the intended purpose, exactly as the situation has always been in the case of
liquid/liquid systems. On the contrary, still now, for systems comprising supercritic
gases put into contact with liquids, no data are available, which may be comparable
to the data available for liquid/liquid systems.
[0014] Therefore, the purpose of the present invention is a novel process for extracting
apolar substances from a liquid phase which contains them, which process enables the
drawbacks which affect the prior art -- as briefly outlined above -- to be overcome.
[0015] In particular, a first aspect of the present invention is a process for extracting
apolar compounds from mixtures which contain them, by using a fluid under supercritic
conditions, which acts in countercurrent in a tower of new conception, containing
a series of perforated trays particularly suitable for such types of extractions.
[0016] A further aspect of the instant invention is a particular type of extraction tower
which can be used in the above mentioned extraction process.
[0017] According to as disclosed in greater detail in the following examples, the novel
process makes it possible high purities to be achieved of the products to be separated,
together with high extraction yields and high efficiencies, as referred to the used
amount of critic gas.
[0018] In particular, according to the method of the present invention the extracting fluid
is fed, under temperature and pressure conditions which exceed the critic conditions
of said extraction fluid, to the bottom of the extraction tower, which contains a
series of perforated trays -- an example of practical embodiment of which is disclosed
in the following -- and from the top of the tower the heavier, liquid mixture to be
submitted to extraction is fed under countercurrent flow conditions.
[0019] If supercritic fluid is CO₂, which, as said, showed to be particularly suitable for
the extraction of n-paraffins from their mixtures with sulfonated paraffins, it is
necessary to operate under temperature and pressure conditions respectively higher
than 35°C and 120 atm. An example of extraction tower which, as said, constitutes
an integrant aspect of the present invention, is disclosed in the hereto attached
figures 1 and 2. The experimental tests reported in the following were carried out
by using such a column shown in figures 1 and 2.
[0020] Of course, although it constitutes an integrant part of the present invention, the
tower shown in said figures should not be understood as being limitative of the scope
of the same invention. Other models of extraction tower can be accomplished in order
to carry out the extraction process according to the present invention, but such models
and their use should be considered dependent from, when not already included in, the
definition of the invention as reported in the instant disclosure.
[0021] Referring to Figures 1 and 2, the tower consists of a high-pressure tube closed at
its ends by flat flanges and provided with the necessary side fittings. Along a portion
of said tube the trays are installed and kept in position by means of thin-wall tubular
spacer elements whose outer diameter is slightly lower than the inner diameter of
the tube which constitutes the tower.
[0022] In Figure 2 (in which the extraction tower is schematically shown), the line indicated
with the reference numeral 1 represents in particular the capacitive sensor; the line
2 represents the position of the level of the liquid mass; the presence of 10 trays
is hypothesized as well.
[0023] All trays are equal, and are installed alternatively rotated by 180° to each other;
an extraction tray is shown in Figure 1, in which also the sizes are reported, which
were used in order to carry out the practical tests, as disclosed in detail in the
following: the bores provided in the trays have a diameter comprised within the range
of from 2 to 15 mm.
[0024] Figure 3 shows in its turn an operative diagram to which reference may be made in
order to understand the experimental examples disclosed in the following.
[0025] In said Figure, 1 represents CO₂ inlet, 2 is the extract outlet line, 3 is the feed
line through which the stream to be submitted to the extraction treatment is fed to
the tower, 4 is point were the refined product (SASA) is collected; PC is is the pressure
control and LC is the level control For experimental purposes, a tower of 50 mm of
diameter was used, which was equipped with trays of AISI 904L with 2 holes of 5 mm
and a downcomer of 10 mm of diameter (Figure 1). The continuous phase flows downwards
along the downcomer.
[0026] The dispersed phase rises by flowing through the tray bores.
[0027] Under these conditions, the dispersed phase gets splitted up into bubbles which in
the region under the successive tray form again a continuous phase
[0028] Along the tower, 10 trays are installed, at mutual distances of about 150 mm.
[0029] Under these conditions, the supercritic gas turns ten times from a continuous phase
into a subdivided phase; on considering the height of the liquid column which has
to be maintained under the holes, the stretch along which the contact occurs between
the liquid phase and the dispersed gas is at least 100 mm long.
[0030] A series of tests were carried out under different conditions; some of the most significant
of them are reported in the following.
Operating conditions |
* Pressure |
150 bar |
* Temperature |
45°C |
* Continuous SASA phase/high level |
|
Composition of stream fed to tower |
|
% by weight |
* SASA |
40 |
* NP |
50 |
* H₂O + H₂SO₄ |
10 |
Flowrates of entering and leaving streams (Figure 3) |
1. CO₂ |
10 kg/hour |
2. Extract |
11.15 kg/hour |
CO₂ |
10 do. |
nP |
1.13 do. |
3. Feed |
2.50 kg/hour |
SASA |
1 do. |
nP |
1.25 do. |
H₂O + H₂SO₄ |
0.25 do. |
4. Refined product |
1.35 kg/hour |
SASA |
1 do. |
nP |
1.12 do. |
H₂O + H₂SO₄ |
0.25 do. |
[0031] The concentrations are respectively expressed as ratios of nP to CO₂ and of nP to
SASA.
[0032] From Figure 4, 2.7 theoretical trays result, which correspond to an efficiency of
27% per each tray.
Operating conditions |
* Pressure |
150 bar |
* Temperature |
45°C |
* Continuous SASA phase/high level |
|
Composition of stream fed to tower |
(The refined stream from 1 was used) |
|
% by weight |
* SASA |
73 |
* NP |
9 |
* H₂O + H₂SO₄ |
18 |
Flowrates of entering and leaving streams (Figure 3) |
1. CO₂ |
10 kg/hour |
2. Extract |
10.11 kg/hour |
CO₂ |
10 do. |
nP |
0.11 do. |
3. Feed |
1.37 kg/hour |
SASA |
1 do. |
nP |
0.12 do. |
H₂O + H₂SO₄ |
0.25 do. |
4. Refined product |
1.26 kg/hour |
SASA |
1 do. |
H₂O + H₂SO₄ |
0.25 do. |
nP |
0.012 do. |
[0033] The concentrations are respectively expressed as ratios of nP to CO₂ and of nP to
SASA.
[0034] From Figure 5, 2.5 theoretical trays result, which correspond to an efficiency of
25% per each tray.
[0035] From the above examples, it results that a high-purity SASA (purity level of about
99%) can be reached with the use of 10 trays and two extractions in cascade.
[0036] In Figure 6, the behaviour of one single tower is reported; in order to obtain the
same result by means of one single extraction, approximately 6 theoretical trays,
i.e., 25 actual trays have to be used, resulting in a height of 3,750 mm, easy accomplished:
the dotted line "A" relates to test No. 1, the solid line "B" relates to test No.
2.
[0037] With the above indicated flowrates, a throughput of 1 kg/hour of purified SASA per
20 cm² of column is obtained; a column having a diameter of 500 mm would enable a
production rate of not less than 200 kg/h of purified SASA to be obtained with a continuous
process.
[0038] In order to practice the present invention at an industrial level the same intallation
scheme could be maintained, with multi-passage trays being possibly provided in case
of large-diameter towers.
1. Process for extracting an apolar substance from a polar substance in the liquid
phase, which consists of putting the liquid phase which contains the substance to
be extracted into contact with a supercritic gas flowing in counter-corrent in an
extraction tower with perforated trays.
2. Process for extracting an apolar substance from a polar substance according to
the preceding claim, in which the supercritic gas is CO₂.
3. Process for extracting an apolar substance from a polar substance according to
claims 1 and 2, in which the liquid phase which contains the substance to be extracted
is a mixture of sulfonic acids, water and H₂SO₄.
4. Process for extracting an apolar substance from a polar substance according to
claims 2 and 3, characterized in that said extraction is carried out in a tower substantially
constituted by a high-pressure tube inside which perforated trays and devices for
controlling the level of the heavy phase, and for discharging it are installed.
5. Process for extracting an apolar substance from a polar substance according to
the preceding claim, in which the tower used in said process is equipped with trays
with holes of from 2 to 15 mm of diameter.
6. Process for extracting an apolar substance from a polar substance according to
the preceding claim, in which the tower used in said process is equipped with all
equal trays, installed alternatively rotated by 180° to each other